CN102675683A - Solvent and catalyst recovery technology in polyphenyl thioether production - Google Patents
Solvent and catalyst recovery technology in polyphenyl thioether production Download PDFInfo
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- CN102675683A CN102675683A CN201110066328XA CN201110066328A CN102675683A CN 102675683 A CN102675683 A CN 102675683A CN 201110066328X A CN201110066328X A CN 201110066328XA CN 201110066328 A CN201110066328 A CN 201110066328A CN 102675683 A CN102675683 A CN 102675683A
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Abstract
The invention relates to a solvent and catalyst recovery technology in polyphenyl thioether production, which comprises the steps of: after polycondensation reaction is finished, firstly adding 1-3mol/mol Na2S and fresh NMP (N-methyl pyrrolidone) solvent as a diluting agent, diluting the reaction system with NMP to obtain another mixture, and further treating the mixture by filtering, extraction, evaporation and spiral evaporator to respectively obtain a mixed solution containing NMP and water and a powder mixture containing a cosolvent and byproducts; and evaporating the mixed solution containing NMP and water to remove water to obtain NMP solvent containing certain impurities, further rectifying and purifying the NMP solvent by a rectifying tower to obtain NMP solvent with the purity of 99.98% and the recovery rate of 96-98%to be recycled for polyphenyl thioether resin synthesis, and treating the powder mixture containing the cosolvent and byproducts to obtain catalyst lithium chloride with the purity of 99.95-99.98% and the recovery rate of 98-99%.
Description
Technical field
The present invention relates to the polyphenylene sulphide production process method improvement.
Background technology
Adopting sodium sulphite and santochlor (P-DCB) is raw material; Polycondensation is produced in the technological process of polyphenylene sulfide (PPS) resin under the effect of basic metal solubility promoter; Need alkali-metal NMP (N-Methyl pyrrolidone) solution to accomplish catalysis at polymerization stage; Compare with the cost of other raw material, NMP and basic metal solubility promoter occupy suitable price proportion, but solvent NMP and solubility promoter are nonexpendable in theory in the production process of PPS; Can therefore, reclaim with the higher recovery be the key that reduce the PPS production cost with solubility promoter still.
After polyreaction is accomplished; The 65-70% of NMP can reclaim through the method for routine, but remaining 25-30% and solubility promoter combine and stayed in the residue, and this residue is the sosoloid that is similar to complex compound; Boiling point 150-160; Extremely difficult the separation,, also can't this part NMP be reclaimed even under vacuum condition.
Introduced solvent and solubility promoter recovery technology in a kind of polyphenylene sulfide production at one Chinese patent application number CN001161423; But pondered-over is to adopt carbonate to reclaim so-called catalyzer; Yet in fact low the getting of the recovery of this catalyzer dare not let the people flatter really; Its catalyst recovery is very low generally between 5-10%wt, and the solubility promoter of returning can not utilize at all again.
In USP number US5711873, introduce the recovery technology of the solvent of polyphenylene sulfide production; Though this technology adopts the thinner of low boiling point solvent as reaction system, though in reaction system, add the filtration that low boiling point organic solvent helps reaction mixture, and also easy recovery and purification of low boiling point solvent; But; To having relatively high expectations of the material of polymerization reaction kettle,, can increase the pressure of reaction kettle if add in the later stage of reaction system; Also take simultaneously and carve the attentive response still and surpass design and bear pressure, cause serious accident because of carelessness like this.
In USP number US6437024, introduced and adopted methyl alcohol to be used as extracting the extraction agent of oligopolymer in the polyphenylene sulfide, ring compound, nmp solvent and by product alkali metal halide; This by product should be a lithium chloride therein, and it is that the employing lithium sulfide is polyphenylene sulfide synthetic starting material.
Above shortcoming in view of prior art; The objective of the invention is to create a kind of polyphenylene sulfide produce in the novel method that reclaims of solvent and solubility promoter, make to be able to high-recovery with residual that part of NMP of sosoloid form and solubility promoter and to reclaim, to reduce the production cost of PPS; The NMP that returns simultaneously and the purity of solubility promoter all are very high; We can say the level that meets or exceeds external similar retrieving arrangement, and adopt spiral evaporator to solve the dope that produces in solvent and the solubility promoter removal process, this dope is solubility promoter lithium chloride crystal in fact; Adopting the purpose of spiral evaporator is the strong shearing through this equipment; Reduce the viscosity of dope, reaching is that NMP wherein is or/and moisture content or/and methyl alcohol extremely is easy to be evaporated, helps improving the recovery and the purity of nmp solvent and solubility promoter lithium chloride.
Though the present invention adopts high boiling solvent to be used as the thinner of reaction system; But; Also can be than adopting low boiling point organic solvent to obtain the purity height of polyphenylene sulfide; Because a lot of oligopolymer and ring compound are easy to be dissolved in the nmp solvent; For this reason, the present invention can only be used to methyl alcohol to dissolve and reclaims little amount of N MP and as the solvent that dissolves lithium chloride, and the present invention to adopt NMP be that thinner is at first removed oligopolymer and ring compound and a large amount of solubility promoter lithium chlorides in the polyphenylene sulfide; Therefore it is a kind of reasonable to the objective of the invention is to utilize, and advantages of simplicity and high efficiency technical process route comes nmp solvent and the solubility promoter lithium chloride in the poly-p-phenylene sulfide ether resin technological process of production to reclaim.
Summary of the invention
Deficiency in view of prior art the objective of the invention is, and solvent and catalyst recovery technology in a kind of polyphenylene sulfide production are provided, and advantages of simplicity and high efficiency realizes that nmp solvent and the solubility promoter lithium chloride in the poly-p-phenylene sulfide ether resin technological process of production reclaims.
Its concrete grammar is: adopting many water cure sodium and santochlor is raw material; Produce polyphenylene sulfide through process steps such as dehydration, polycondensations; It is characterized in that, be catalyzer with the metal halide salt, should be solubility promoter (all expressing with solubility promoter later on) in fact; After polycondensation is accomplished, relate to the solvent of polyphenylene sulfide production and the recovery of solubility promoter etc., its Technology comprises:
1, in reaction system, add fresh nmp solvent and be used as thinner, add-on is 1-3mol/ molNa
2S; Thereby form the mixture that contains polyphenylene sulfide, NMP, solubility promoter lithium chloride, water and by product; The vertical whizzer that vacuumizes of its mixture input is carried out solid-liquid separation; Obtain containing polyphenylene sulfide and part by product with the wet solid matter of little amount of N MP, and the filtrating of containing NMP, water, solubility promoter lithium chloride and part by product sodium-chlor.
2,1 resulting filtrating is steamed the mixture of NMP and moisture through underpressure distillation; Residuum is the dope that contains solubility promoter and by product and little amount of N MP and moisture content bottom the decompression separation device; Become the mixing liquid that contains NMP and water through overcooling, it is for use to mix liquid input wet tank.
3, with 2) dope that obtains further evaporates away wherein NMP and moisture with the spiral evaporator that the worm conveyor input has star-like feeder; Through the mixing liquid storage tank of supercooler cooling input NMP and water, from the powdery solubility promoter of spiral evaporator discharge and the mixture of by product.The screw diameter of the spiral evaporator of using is 75; Length-to-diameter ratio is 70-80; Adopt the thermal oil thermostatically heating, Heating temperature is the highest can be reached 250-260 ℃ 3 diameters are installed above spiral is the 85-90mm venting port, and NMP and water vapour are that the employing vacuum pump vacuumizes discharge.
4, with 1 obtain contain polyphenylene sulfide and part by product adopt methanol extraction three times with the wet solid matter of little amount of N MP; Filter; Mainly be the mixing solutions that contains methyl alcohol and NMP and moisture in the filtrating, then its mixing solutions imported an other distillation tower and distill that what come out from the distillation tower top is methanol steam; This steam utilizes through the overcooling purifying again, and the water vapour that flows out from the distillation tower middle and upper part reclaims the washing of the polyphenylene sulfide that is used for the back through cooling.
The NMP that flows out from the distillation tower bottom, for use through input NMP and water mixed liquid body storage tank after the processing under cooling.
5, with 2), 3), 4) and the NMP that obtains and water mixed liquid body and function pump input solvent recuperation distillation tower; What come out from the distillation tower overhead stream is moisture content; This moisture reclaims the washing that is used for polyphenylene sulfide through cooling, and what flow out from the distillation tower bottom is nmp solvent, and this nmp solvent input rectifying tower is further purified; Effusive purity is 99.98% nmp solvent from the rectifying tower top, and the recovery is 96-98%.
6, with 3) solubility promoter that obtains and the meal of by product; Add industrial grade benzenemethanol; Making the solids concn of its pulverulent mixture in methanol solvate is 15-20%wt, through its solubility promoter fully is dissolved among the methyl alcohol, then through filtering for three times repeatedly; After dissolving, the filtration, three times filtrating combines for use; Solids remaining on the strainer is the wet mixture that contains by product and methyl alcohol, and this mixture is removed methyl alcohol through heating evaporation, and methanol steam is through the cooling recycling.
7, with 6) another evaporator evaporation of filtrating input removes methyl alcohol; From the remaining viscous mixture that contains methyl alcohol and solubility promoter of base of evaporator; The spiral evaporator that this dope adopts the worm conveyor input to have star-like feeder is further evaporated away wherein remaining methyl alcohol; The methanol steam that is evaporated from spiral evaporator is through the cooling recycling, and what eject from the spiral evaporator head is the solubility promoter powder, and this powder is the catalyzer of returning.Purity is 99.95-99.98%; The recovery is 98-99%; The screw diameter of the spiral evaporator of its application is 158, and length-to-diameter ratio is 50-60, adopts the thermal oil thermostatically heating; Heating temperature is the highest can be reached 150-160 ℃ 3 diameters are installed above spiral is the 55-60mm venting port, and methanol gas is to adopt vacuum pump to vacuumize discharge.
The present invention is in order to reach the purpose of invention; Adopt spiral evaporator to containing little amount of N MP and moisture content or containing small amount of methanol and the thick material of the lithium chloride of moisture content and sodium-chlor further evaporates wherein NMP or moisture content or methyl alcohol; Thereby make big blocky lithium chloride under the shearing of spiral, become fine powder; So promptly solved and adopted so-called thin-film evaporator drying to come out to be big blocky material; Solve the inefficient problem of thin-film evaporator again, simultaneously, also solved the NMP that is evaporated or the recovery problem of water vapour or methanol steam.
It is raw material that the present invention adopts many water cure sodium and p-Xylol, produces polyphenylene sulfide through process steps such as dehydration, polycondensations.With basic metal halide salt lithium chloride is solubility promoter, after polycondensation is accomplished, adds 1-3mol/ molNa earlier
2S; Fresh nmp solvent is as thinner; Make reaction system under the dilution of NMP, obtain another mixture again; This mixture is through obtaining containing the wet mixture of polyphenylene sulfide and solubility promoter lithium chloride and by product sodium-chlor and less water and nmp solvent after filtering; This mixture is that water and NMP and solubility promoter lithium chloride in the mixture forms the mixing solutions that contains water and NMP and solubility promoter lithium chloride with methanol extraction, and this solution is removed most water and NMP and methyl alcohol through evaporator evaporation, again with after the further processing of spiral evaporator; Obtain containing the mixing solutions of NMP and moisture respectively, and the pulverulent mixture that contains solubility promoter and by product.
And filtrating being that reaction system filters out contained the mixed solution of water and NMP and solubility promoter lithium chloride and part by product sodium-chlor; This mixed solution removes most water through evaporator evaporation and NMP forms a kind of thick mixture; After further handling with spiral evaporator again; Obtain containing the mixing solutions of NMP and moisture respectively, and the pulverulent mixture that contains solubility promoter and by product.
The mixing solutions that contains NMP and water is removed moisture content through pervaporation; Obtain containing the nmp solvent of certain impurity; It is that 99.98% nmp solvent is used in the synthetic of polyphenylene sulfide again that this nmp solvent obtains purity through the further rectification and purification of rectifying tower, and the recovery of nmp solvent is 96-98%.
After the pulverulent mixture that solubility promoter and by product arranged repeatedly dissolves solubility promoter through methyl alcohol again; Filter; Filtrating obtains a kind of dope that contains methyl alcohol after pervaporation is removed most methyl alcohol, dope vacuumizes through spiral evaporator and removes methyl alcohol; Obtaining purity is 99.95-99.98%, and the recovery is the catalyzer lithium chloride (solubility promoter) of 98-99%.
The solubility promoter and the process method that adopt the present invention to select; Can reclaim being decomposed by NMP and the thick sosoloid of solubility promoter when the polycondensation, obtain NMP and corresponding solubility promoter respectively, wherein the recovery of NMP can reach 96-98%; Practice thrift raw material, reduced the production cost of PPS.
Embodiment
1) in polyphenylene sulfide synthetic reaction system, added a certain amount of nmp solvent before this as thinner; Then the reaction system mixture is carried out filtering separation; Filtrating is gone out through evaporation and is formed a kind of thick material behind most NMP and the moisture content; After thick material is removed NMP and moisture content through the further evaporation process of spiral evaporator, thereby become flour, NMP and moisture content input storage tank are pending; And the filter cake that the reaction system filtration produces adds the wherein residual NMP of a certain amount of methanol extraction and the moisture content and the lithium chloride completely that is untreated; Then its evaporation is gone out and form a kind of thick material behind most NMP and moisture content and the methanol solvate; After this thick material process spiral evaporator is handled and removed NMP and moisture content, thereby become flour; NMP and moisture content input storage tank are pending.
2) with 1) the methyl alcohol NMP that obtains and the mixing solutions of moisture content through evaporation separates remove methyl alcohol, moisture content after, it is pending that residual NMP imports storage tank.
3) with 1) flour that obtains adds a certain amount of methyl alcohol, make wherein lithium chloride fully be dissolved among the methyl alcohol after, remove by filter undissolved by product sodium-chlor.Contain lithium chloride and methyl alcohol in the filtrating, behind the most methyl alcohol of pervaporation, form a kind of thick material, this material adopts spiral evaporator further to evaporate and removes methyl alcohol, and discharging meal from the spiral evaporator head is exactly the lithium chloride of returning.
4) with 1) and 2) NMP that obtains and moisture content after pervaporation is removed moisture content, again NMP is imported rectifying tower NMP is carried out rectification and purification, solvent recuperation used in the polyphenylene sulfide production process is returned to utilize again like this.
The embodiment that the present invention is concrete.
Embodiment 1
1) LiCl and the nmp solution 12Kg of adding 600g in polyreaction add 3kg (1mol/ molNa after polycondensation is accomplished
2S) fresh nmp solvent is used as thinner; Thereby form the mixture that contains polyphenylene sulfide, NMP, solubility promoter, water and by product; The vertical whizzer that vacuumizes of its mixture input is carried out solid-liquid separation; Obtain containing polyphenylene sulfide and part by product with the wet solid matter of little amount of N MP, and the filtrating of containing NMP, water, solubility promoter and part by product.
2) 1 resulting filtrating is steamed the mixture of NMP and moisture through underpressure distillation; Residuum is the dope that contains solubility promoter and by product and little amount of N MP and moisture content bottom the decompression separation device; Become the mixing liquid that contains NMP and water through overcooling, it is for use to mix liquid input wet tank.
3) with 2) dope that the obtains spiral evaporator screw diameter that uses the worm conveyor input to have star-like feeder is 75; Length-to-diameter ratio is 70; Adopt the thermal oil thermostatically heating; Heating temperature is the highest can be reached 260 ℃ 3 diameters are installed above spiral is the 90mm venting port; NMP and water vapour are that the employing vacuum pump vacuumizes further wherein NMP and the moisture of evaporating away of discharge, through the mixing liquid storage tank of supercooler cooling input NMP and water, from the powdery solubility promoter of spiral evaporator discharge and the mixture of by product.
4) with 1 obtain contain polyphenylene sulfide and part by product adopt methanol extraction three times with the wet solid matter of little amount of N MP; Filter; Mainly be the mixing solutions that contains methyl alcohol and NMP and moisture in the filtrating, then its mixing solutions imported an other distillation tower and distill that what come out from the distillation tower top is methanol steam; This steam utilizes through the overcooling purifying again, and the water vapour that flows out from the distillation tower middle and upper part reclaims the washing of the polyphenylene sulfide that is used for the back through cooling.
The NMP that flows out from the distillation tower bottom, for use through input NMP and water mixed liquid body storage tank after the processing under cooling.
5) with 2), 3), 4) and the NMP that obtains and water mixed liquid body and function pump input solvent recuperation distillation tower; What come out from the distillation tower overhead stream is moisture content; This moisture reclaims the washing that is used for polyphenylene sulfide through cooling, and what flow out from the distillation tower bottom is nmp solvent, and this nmp solvent input rectifying tower is further purified; Effusive purity is 99.98% nmp solvent from the rectifying tower top, and the recovery is 96%.
6), with 3) solubility promoter that obtains and the meal of by product; Add industrial grade benzenemethanol; Making the solids concn of its pulverulent mixture in methanol solvate is 15%wt, through its solubility promoter fully is dissolved among the methyl alcohol, then through filtering for three times repeatedly; After dissolving, the filtration, three times filtrating combines for use; Solids remaining on the strainer is the wet mixture that contains by product and methyl alcohol, and this mixture is removed methyl alcohol through heating evaporation, and methanol steam is through the cooling recycling.
7), with 6) another evaporator evaporation of filtrating input removes methyl alcohol; From the remaining viscous mixture that contains methyl alcohol and solubility promoter of base of evaporator; The spiral evaporator that this dope adopts the worm conveyor input to have star-like feeder is further evaporated away wherein remaining methyl alcohol; From the spiral evaporator screw diameter is 58, and length-to-diameter ratio is 50, adopts the thermal oil thermostatically heating; Heating temperature is the highest can be reached 160 ℃ 3 diameters are installed above spiral is the 55mm venting port; Methanol gas is to adopt vacuum pump to vacuumize to discharge the methanol steam that is evaporated through the cooling recycling, and what eject from the spiral evaporator head is the solubility promoter powder, and this powder is the catalyzer of returning.Purity is 99.95%, and the recovery is 98%
Embodiment 2
1) LiCl and the nmp solution 12Kg of adding 600g in polyreaction add 6kg (2mol/ molNa after polycondensation is accomplished
2S) fresh nmp solvent is used as thinner; Thereby form the mixture that contains polyphenylene sulfide, NMP, solubility promoter, water and by product; The vertical whizzer that vacuumizes of its mixture input is carried out solid-liquid separation; Obtain containing polyphenylene sulfide and part by product with the wet solid matter of little amount of N MP, and the filtrating of containing NMP, water, solubility promoter and part by product.
2) 1 resulting filtrating is steamed the mixture of NMP and moisture through underpressure distillation; Residuum is the dope that contains solubility promoter and by product and little amount of N MP and moisture content bottom the decompression separation device; Become the mixing liquid that contains NMP and water through overcooling, it is for use to mix liquid input wet tank.
3) with 2) dope that the obtains spiral evaporator screw diameter that uses the worm conveyor input to have star-like feeder is 75; Length-to-diameter ratio is 80; Adopt the thermal oil thermostatically heating; Heating temperature is the highest can be reached 250 ℃ 3 diameters are installed above spiral is the 85mm venting port; NMP and water vapour are that the employing vacuum pump vacuumizes further wherein NMP and the moisture of evaporating away of discharge, through the mixing liquid storage tank of supercooler cooling input NMP and water, from the powdery solubility promoter of spiral evaporator discharge and the mixture of by product.
4) with 1 obtain contain polyphenylene sulfide and part by product adopt methanol extraction three times with the wet solid matter of little amount of N MP; Filter; Mainly be the mixing solutions that contains methyl alcohol and NMP and moisture in the filtrating, then its mixing solutions imported an other distillation tower and distill that what come out from the distillation tower top is methanol steam; This steam utilizes through the overcooling purifying again, and the water vapour that flows out from the distillation tower middle and upper part reclaims the washing of the polyphenylene sulfide that is used for the back through cooling.
The NMP that flows out from the distillation tower bottom, for use through input NMP and water mixed liquid body storage tank after the processing under cooling.
5) with 2), 3), 4) and the NMP that obtains and water mixed liquid body and function pump input solvent recuperation distillation tower; What come out from the distillation tower overhead stream is moisture content; This moisture reclaims the washing that is used for polyphenylene sulfide through cooling, and what flow out from the distillation tower bottom is nmp solvent, and this nmp solvent input rectifying tower is further purified; Effusive purity is 99.98% nmp solvent from the rectifying tower top, and the recovery is 98%.
6), with 3) solubility promoter that obtains and the meal of by product; Add industrial grade benzenemethanol; Making the solids concn of its pulverulent mixture in methanol solvate is 20%wt, through its solubility promoter fully is dissolved among the methyl alcohol, then through filtering for three times repeatedly; After dissolving, the filtration, three times filtrating combines for use; Solids remaining on the strainer is the wet mixture that contains by product and methyl alcohol, and this mixture is removed methyl alcohol through heating evaporation, and methanol steam is through the cooling recycling.
7), with 6) another evaporator evaporation of filtrating input removes methyl alcohol; From the remaining viscous mixture that contains methyl alcohol and solubility promoter of base of evaporator; The spiral evaporator that this dope adopts the worm conveyor input to have star-like feeder is further evaporated away wherein remaining methyl alcohol; From the spiral evaporator screw diameter is 58, and length-to-diameter ratio is 50, adopts the thermal oil thermostatically heating; Heating temperature is the highest can be reached 150 ℃ 3 diameters are installed above spiral is the 60mm venting port; Methanol gas is to adopt vacuum pump to vacuumize to discharge the methanol steam that is evaporated through the cooling recycling, and what eject from the spiral evaporator head is the solubility promoter powder, and this powder is the catalyzer of returning.Purity is 99.98%, and the recovery is 99%
Embodiment 3
1) LiCl and the nmp solution 12Kg of adding 600g in polyreaction add 9kg (3mol/ molNa after polycondensation is accomplished
2S) fresh nmp solvent is used as thinner; Thereby form the mixture that contains polyphenylene sulfide, NMP, solubility promoter, water and by product; The vertical whizzer that vacuumizes of its mixture input is carried out solid-liquid separation; Obtain containing polyphenylene sulfide and part by product with the wet solid matter of little amount of N MP, and the filtrating of containing NMP, water, solubility promoter and part by product.
2) 1 resulting filtrating is steamed the mixture of NMP and moisture through underpressure distillation; Residuum is the dope that contains solubility promoter and by product and little amount of N MP and moisture content bottom the decompression separation device; Become the mixing liquid that contains NMP and water through overcooling, it is for use to mix liquid input wet tank.
3) with 2) dope that the obtains spiral evaporator screw diameter that uses the worm conveyor input to have star-like feeder is 75; Length-to-diameter ratio is 75; Adopt the thermal oil thermostatically heating; Heating temperature is the highest can be reached 255 ℃ 3 diameters are installed above spiral is the 88mm venting port; NMP and water vapour are that the employing vacuum pump vacuumizes further wherein NMP and the moisture of evaporating away of discharge, through the mixing liquid storage tank of supercooler cooling input NMP and water, from the powdery solubility promoter of spiral evaporator discharge and the mixture of by product.
4) with 1 obtain contain polyphenylene sulfide and part by product adopt methanol extraction three times with the wet solid matter of little amount of N MP; Filter; Mainly be the mixing solutions that contains methyl alcohol and NMP and moisture in the filtrating, then its mixing solutions imported an other distillation tower and distill that what come out from the distillation tower top is methanol steam; This steam utilizes through the overcooling purifying again, and the water vapour that flows out from the distillation tower middle and upper part reclaims the washing of the polyphenylene sulfide that is used for the back through cooling.
The NMP that flows out from the distillation tower bottom, for use through input NMP and water mixed liquid body storage tank after the processing under cooling.
5) with 2), 3), 4) and the NMP that obtains and water mixed liquid body and function pump input solvent recuperation distillation tower; What come out from the distillation tower overhead stream is moisture content; This moisture reclaims the washing that is used for polyphenylene sulfide through cooling, and what flow out from the distillation tower bottom is nmp solvent, and this nmp solvent input rectifying tower is further purified; Effusive purity is 99.98% nmp solvent from the rectifying tower top, and the recovery is 97%.
6), with 3) solubility promoter that obtains and the meal of by product; Add industrial grade benzenemethanol; Making the solids concn of its pulverulent mixture in methanol solvate is 18%wt, through its solubility promoter fully is dissolved among the methyl alcohol, then through filtering for three times repeatedly; After dissolving, the filtration, three times filtrating combines for use; Solids remaining on the strainer is the wet mixture that contains by product and methyl alcohol, and this mixture is removed methyl alcohol through heating evaporation, and methanol steam is through the cooling recycling.
7), with 6) another evaporator evaporation of filtrating input removes methyl alcohol; From the remaining viscous mixture that contains methyl alcohol and solubility promoter of base of evaporator; The spiral evaporator that this dope adopts the worm conveyor input to have star-like feeder is further evaporated away wherein remaining methyl alcohol; From the spiral evaporator screw diameter is 58, and length-to-diameter ratio is 55, adopts the thermal oil thermostatically heating; Heating temperature is the highest can be reached 155 ℃ 3 diameters are installed above spiral is the 58mm venting port; Methanol gas is to adopt vacuum pump to vacuumize to discharge the methanol steam that is evaporated through the cooling recycling, and what eject from the spiral evaporator head is the solubility promoter powder, and this powder is the catalyzer of returning.Purity is 99.97%, and the recovery is 98.5%.
Claims (3)
1. solvent during polyphenylene sulfide is produced and catalyst recovery technology, adopting many water cure sodium and santochlor is raw material, produces polyphenylene sulfide through process steps such as dehydration, polycondensations, it is characterized in that, with the metal halide salt catalyzer, Technology comprises:
1) in reaction system, add fresh nmp solvent and be used as thinner, add-on is 1-3mol/ molNa
2S; Thereby form the mixture that contains polyphenylene sulfide, NMP, solubility promoter, water and by product; Mixture is imported the vertical whizzer that vacuumizes carry out solid-liquid separation; Obtain containing polyphenylene sulfide and part by product with the wet solid matter of little amount of N MP, and the filtrating of containing NMP, water, solubility promoter and part by product;
2) 1 resulting filtrating is steamed the mixture of NMP and moisture through underpressure distillation; Residuum is the dope that contains solubility promoter and by product and little amount of N MP and moisture content bottom the decompression separation device; Become the mixing liquid that contains NMP and water through overcooling, it is for use to mix liquid input wet tank;
3) with 2) dope that obtains further evaporates away wherein NMP and moisture with the spiral evaporator that the worm conveyor input has star-like feeder; Through the mixing liquid storage tank of supercooler cooling input NMP and water, from the powdery solubility promoter of spiral evaporator discharge and the mixture of by product;
4) with 1) obtain contain polyphenylene sulfide and part by product adopt methanol extraction three times with the wet solid matter of little amount of N MP; Filtering, mainly is the mixing solutions that contains methyl alcohol and NMP and moisture in the filtrating, then its mixing solutions is imported an other distillation tower and distills; What come out from the distillation tower top is methanol steam; This steam utilizes through the overcooling purifying again, the washing that the water vapour that flows out from the distillation tower middle and upper part reclaims the polyphenylene sulfide that is used for the back through cooling, the NMP that flows out from the distillation tower bottom; For use through input NMP and water mixed liquid body storage tank after the processing under cooling
5) with 2), 3), 4) and the NMP that obtains and water mixed liquid body and function pump input solvent recuperation distillation tower; What come out from the distillation tower overhead stream is moisture content; This moisture reclaims the washing that is used for polyphenylene sulfide through cooling, and what flow out from the distillation tower bottom is nmp solvent, and this nmp solvent input rectifying tower is further purified; Effusive purity is 99.98% nmp solvent from the rectifying tower top, and the recovery is 96-98%;
6), with 3) solubility promoter that obtains and the meal of by product; Add industrial grade benzenemethanol; Making the solids concn of its pulverulent mixture in methanol solvate is 15-20%wt, through its solubility promoter fully is dissolved among the methyl alcohol, then through filtering for three times repeatedly; After dissolving, the filtration, three times filtrating combines for use; Solids remaining on the strainer is the wet mixture that contains by product and methyl alcohol, and this mixture is removed methyl alcohol through heating evaporation, and methanol steam is through the cooling recycling;
7), with 6) another evaporator evaporation of filtrating input removes methyl alcohol; From the remaining viscous mixture that contains methyl alcohol and solubility promoter of base of evaporator; The spiral evaporator that this dope adopts the worm conveyor input to have star-like feeder is further evaporated away wherein remaining methyl alcohol; The methanol steam that is evaporated from spiral evaporator is through the cooling recycling, and what eject from the spiral evaporator head is the solubility promoter powder, and this powder is the catalyzer of returning; Purity is 99.95-99.98%, and the recovery is 98-99%.
2. solvent and catalyst recovery technology in producing according to the said polyphenylene sulfide of claim 1; It is characterized in that said metal halide salt as solubility promoter is LiCl, the screw diameter of the spiral evaporator of its application is 158; Length-to-diameter ratio is 50-60; Adopt the thermal oil thermostatically heating, Heating temperature is the highest can be reached 150-160 ℃ 3 diameters are installed above spiral is the 55-60mm venting port, and methanol gas is to adopt vacuum pump to vacuumize discharge.
3. solvent and catalyst recovery technology in producing according to the said polyphenylene sulfide of claim 1 (3); It is characterized in that; The screw diameter of the spiral evaporator of using is 175, and length-to-diameter ratio is 70-80, adopts the thermal oil thermostatically heating; Heating temperature is the highest can be reached 250-260 ℃ 3 diameters are installed above spiral is the 85-90mm venting port, and NMP and water vapour are to adopt vacuum pump to vacuumize discharge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110066328XA CN102675683B (en) | 2011-03-18 | 2011-03-18 | Solvent and catalyst recovery technology in polyphenyl thioether production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110066328XA CN102675683B (en) | 2011-03-18 | 2011-03-18 | Solvent and catalyst recovery technology in polyphenyl thioether production |
Publications (2)
| Publication Number | Publication Date |
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| CN102675683A true CN102675683A (en) | 2012-09-19 |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447480A (en) * | 2014-11-06 | 2015-03-25 | 中国科学院过程工程研究所 | Continuous recycling method of NMP (N-methyl pyrrolidone) solvent for polyphenylene sulfide production device |
| CN104877167A (en) * | 2015-06-02 | 2015-09-02 | 敦煌西域特种新材股份有限公司 | Method for recycling additive lithium chloride in polyphenylene sulfide resin production process |
| CN104892971A (en) * | 2015-06-02 | 2015-09-09 | 敦煌西域特种新材股份有限公司 | Method for recycling solvent NMP in polyphenylene sulfide resin production process |
| CN105218816A (en) * | 2015-11-05 | 2016-01-06 | 包头市汇智工程咨询有限责任公司 | A kind of resin leaching technology produced for poly arylidene thio-ester resinoid |
| CN106366030A (en) * | 2016-10-12 | 2017-02-01 | 南京大学 | High-purity recycling process system of complex chemical waste liquid |
| CN106395862A (en) * | 2016-08-29 | 2017-02-15 | 四川理工学院 | Recovery method of by-product sodium chloride in production process of polyphenylene sulfide |
| CN106432652A (en) * | 2016-10-20 | 2017-02-22 | 四川大学 | Method for recycling metal catalyst from aramid or polyarylether reaction slurry and application |
| CN106478481A (en) * | 2016-10-08 | 2017-03-08 | 南京大学 | Waste water ultra-pure separation and purification technique of methyl pyrrolidone containing N and paracide |
| CN106565581A (en) * | 2016-10-21 | 2017-04-19 | 天津科技大学 | A method for comprehensive recovery and utilization of lithium containing mixed salts in a polyphenylene sulfide production process |
| CN106565956A (en) * | 2016-10-21 | 2017-04-19 | 天津科技大学 | Method for comprehensive recycling of by-product slurry in polyphenylene sulfide productive process |
| CN107827128A (en) * | 2017-11-16 | 2018-03-23 | 新疆中泰新鑫化工科技股份有限公司 | The recovery method of lithium chloride in oligomer |
| CN107936288A (en) * | 2017-11-30 | 2018-04-20 | 珠海长先新材料科技股份有限公司 | A kind of method of NMP and LiCl in the recycling polyphenylene sulfide production by solvent extraction process technology |
| CN107983393A (en) * | 2017-12-29 | 2018-05-04 | 内蒙古聚贤化工材料科技有限公司 | A kind of method that lithium chloride is recycled in the production for polyphenylene sulfide |
| CN111004393A (en) * | 2019-12-17 | 2020-04-14 | 重庆聚狮新材料科技有限公司 | Washing water circulation process for polyphenylene sulfide production |
| CN111170511A (en) * | 2020-02-13 | 2020-05-19 | 四川明道和化学新材料有限公司 | Treatment method of sodium sulfide azeotropic dehydration liquid rectifying tower produced water |
| CN114949903A (en) * | 2022-06-14 | 2022-08-30 | 山东明化新材料有限公司 | Parallel polyarylene sulfide resin production solvent and catalyst separation and recovery system and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104447480A (en) * | 2014-11-06 | 2015-03-25 | 中国科学院过程工程研究所 | Continuous recycling method of NMP (N-methyl pyrrolidone) solvent for polyphenylene sulfide production device |
| CN104447480B (en) * | 2014-11-06 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of nmp solvent continuous recovery method of polyphenylene sulfide process units |
| CN104877167A (en) * | 2015-06-02 | 2015-09-02 | 敦煌西域特种新材股份有限公司 | Method for recycling additive lithium chloride in polyphenylene sulfide resin production process |
| CN104892971A (en) * | 2015-06-02 | 2015-09-09 | 敦煌西域特种新材股份有限公司 | Method for recycling solvent NMP in polyphenylene sulfide resin production process |
| CN104877167B (en) * | 2015-06-02 | 2018-02-23 | 敦煌西域特种新材股份有限公司 | The method that adjuvant used lithium chloride recycles in polyphenylene sulfide resin production process |
| CN104892971B (en) * | 2015-06-02 | 2017-04-26 | 敦煌西域特种新材股份有限公司 | Method for recycling solvent NMP in polyphenylene sulfide resin production process |
| CN105218816A (en) * | 2015-11-05 | 2016-01-06 | 包头市汇智工程咨询有限责任公司 | A kind of resin leaching technology produced for poly arylidene thio-ester resinoid |
| CN106395862B (en) * | 2016-08-29 | 2017-12-26 | 四川理工学院 | The recovery method of byproduct sodium chloride in a kind of polyphenylene sulfide production process |
| CN106395862A (en) * | 2016-08-29 | 2017-02-15 | 四川理工学院 | Recovery method of by-product sodium chloride in production process of polyphenylene sulfide |
| CN106478481A (en) * | 2016-10-08 | 2017-03-08 | 南京大学 | Waste water ultra-pure separation and purification technique of methyl pyrrolidone containing N and paracide |
| CN106478481B (en) * | 2016-10-08 | 2018-07-06 | 南京大学 | The ultra-pure separation and purification technique of waste water containing N-Methyl pyrrolidone and paracide |
| CN106366030A (en) * | 2016-10-12 | 2017-02-01 | 南京大学 | High-purity recycling process system of complex chemical waste liquid |
| CN106432652A (en) * | 2016-10-20 | 2017-02-22 | 四川大学 | Method for recycling metal catalyst from aramid or polyarylether reaction slurry and application |
| CN106565956A (en) * | 2016-10-21 | 2017-04-19 | 天津科技大学 | Method for comprehensive recycling of by-product slurry in polyphenylene sulfide productive process |
| CN106565581A (en) * | 2016-10-21 | 2017-04-19 | 天津科技大学 | A method for comprehensive recovery and utilization of lithium containing mixed salts in a polyphenylene sulfide production process |
| CN106565956B (en) * | 2016-10-21 | 2018-09-28 | 天津科技大学 | By-product slurry comprehensive reutilization method in a kind of polyphenylene sulfide production process |
| CN106565581B (en) * | 2016-10-21 | 2019-07-12 | 天津科技大学 | The comprehensive reutilization method of mixed salt containing lithium in a kind of polyphenylene sulfide production process |
| CN107827128A (en) * | 2017-11-16 | 2018-03-23 | 新疆中泰新鑫化工科技股份有限公司 | The recovery method of lithium chloride in oligomer |
| CN107936288A (en) * | 2017-11-30 | 2018-04-20 | 珠海长先新材料科技股份有限公司 | A kind of method of NMP and LiCl in the recycling polyphenylene sulfide production by solvent extraction process technology |
| CN107983393A (en) * | 2017-12-29 | 2018-05-04 | 内蒙古聚贤化工材料科技有限公司 | A kind of method that lithium chloride is recycled in the production for polyphenylene sulfide |
| CN111004393A (en) * | 2019-12-17 | 2020-04-14 | 重庆聚狮新材料科技有限公司 | Washing water circulation process for polyphenylene sulfide production |
| CN111170511A (en) * | 2020-02-13 | 2020-05-19 | 四川明道和化学新材料有限公司 | Treatment method of sodium sulfide azeotropic dehydration liquid rectifying tower produced water |
| CN111170511B (en) * | 2020-02-13 | 2021-11-23 | 四川明道和化学新材料有限公司 | Treatment method of sodium sulfide azeotropic dehydration liquid rectifying tower produced water |
| CN114949903A (en) * | 2022-06-14 | 2022-08-30 | 山东明化新材料有限公司 | Parallel polyarylene sulfide resin production solvent and catalyst separation and recovery system and method |
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